JPH03198040A - Production of silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To attain low fog, high sensitivity and high contrast and to suppress changes of photographic characteristics due to mechanical pressure by using an aq. soln. contg. at least two kinds of halide ions selected among chloride ion, bromide ion and iodide ion and continuously varying the ratio between the amts. of the halide ions added with the lapse of time. CONSTITUTION:An aq. soln. 4 of a water soluble silver salt is mixed with an aq. soln. 5 of water soluble halides in a mixer 7 set at the outside of a reactor 1 for forming nuclei and/or growing crystals to form fine silver halide particles, these particles are added to the reactor 1 and nuclei are formed and/or crystals are grown. In this case, at least two kinds of halide ions selected among chloride ion, bromide ion and iodide ion are contained in the aq. soln. 5 and the ratio between the amts. of the halide ions added is continuously varied with the lapse of time. The uniformity of mixed crystals is improved, changes of photographic characteristics due to mechanical pressure is suppressed and the photographic characteristics can be made nearly independent of conditions in development.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a silver halide emulsion useful in the field of photography. More specifically, the present invention relates to a method for producing a silver halide emulsion containing photographically useful silver halide crystal grains such as silver iodobromide, silver chlorobromide, silver chloroiodobromide, and silver iodochloride.

(Prior Art) In the preparation of silver halide grains used in silver halide photographic materials, it is an important issue to take advantage of the strengths of silver iodide, silver bromide, and silver chloride and how to minimize their weaknesses. , and many efforts have been made for this purpose. A mixture of silver iodide, silver bromide, and silver chloride is used to control photographically important factors such as light absorption, adsorption of additives, suitability for chemical sensitization, latent image formation efficiency, and developability. Not only have crystals been used, but efforts have also been made to vary the composition depending on the location within each individual silver halide grain.

As can be seen from the above description, the method for preparing silver halide mixed crystal grains is an important technical field in the preparation of silver halide photographic materials. Previously, silver halide grains having a completely uniform distribution of silver iodide in a silver halide phase containing 3 mol% or more of silver iodide were disclosed in JP-A-1183644 and JP-A-1-183645. There is. In addition, Japanese Patent Application No. 1983-1984 concerning silver halide grains in which the distribution of silver chloride in the silver halide phase containing 10 mol% or more of silver chloride is completely uniform.
No. 861 and No. 63-194862. Furthermore, the silver halide grains are composed of at least one phase containing at least two types of silver halide inside the grains, the halide distribution is completely uniform, and the surfaces of the grains are adjacent to the grains. Japanese Patent Application No. 1-33541 discloses silver halide grains in which the internal composition of silver halide is different from that of silver halide. All of these are due to new silver halide grain manufacturing methods in which the halogen distribution in the mixed crystal is completely uniform, and as described in each, conventional methods. It exhibits superior features such as higher sensitivity compared to silver halide grains produced by silver halide. However, silver halide photographic materials using silver halide grains obtained by these methods have large fluctuations in photographic properties due to changes in development conditions as well as changes in photographic properties due to mechanical pressure, and further improvement is required. was found to be necessary.

JP-A-1-259350 discloses that the interior of the grain consists essentially of silver iodobromide containing 10 mol% or more of silver iodide, and
Disclosed is a silver halide grain that includes at least a grain outer shell made of silver iodobromide containing ~7 mol% of silver iodide, and in which the grain interior and the grain outer shell do not have a clear layered structure. There is.

Among them, "not having a clear layered structure" means that the diffraction curve in X-ray diffraction has substantially one diffraction peak. However, within the scope of the invention, it is difficult to bring the ratio of the high iodine content phase and the low iodine content phase close to each other, and one must rely on one or the other, and as a result, the ratio must be lowered. On the other hand, the performance based on the silver iodobromide phase cannot be fully exploited. In addition, the publication does not mention any means for improving the uniformity of the mixed crystal and eliminating the non-uniformity of PAg in the reaction vessel in which silver halide grains grow, and these problems may lead to poor performance. No mention is made of any decline.

(Problems to be Solved by the Invention) The present invention provides a halogen that has low fog, high sensitivity, hard gradations, and small changes in photographic properties due to mechanical pressure, or small fluctuations in photographic properties due to changes in developing conditions. The purpose is to produce silver oxide emulsions.

(Means for Solving the Problems) As a result of intensive studies, it has been found that the present invention can be achieved by the following configuration.

That is, the present invention involves adding fine-sized silver halide grains to a reaction vessel in which light-sensitive silver halide grains contained in a silver halide photographic emulsion cause nucleation and/or crystal growth of the grains. The photosensitive silver halide grains are obtained by nucleation and/or crystal growth in the reaction vessel by nucleation and/or crystal growth in the reaction vessel, and the fine-sized silver halide grains are used for nucleation of the photosensitive silver halide grains. and/or formed by mixing an aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide in a mixer provided outside the reaction vessel in which crystal growth occurs, and immediately fed into the reaction vessel after formation. The halide ions contained in the water-soluble halide aqueous solution contain at least chloride ions, bromide ions, and iodide ions. A method for producing a silver halide photographic emulsion comprising the step of continuously changing the ratio of the amounts of at least two halide ions added over time.

Specific means for implementing the present invention will be described below.

mixing an aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide to form fine-sized silver halide particles in a mixer provided outside the reaction vessel in which nucleation and/or crystal growth occurs; A method for causing nucleation and/or crystal growth by adding this to the reaction vessel has already been described in detail in Japanese Patent Application Laid-Open No. 1-183644, etc., and this system is also used in the present invention.

A system for such a particle formation method is shown below using FIG. 1 as an example.

In FIG. 1, a reaction vessel 1 first contains an aqueous protective colloid solution 2. In FIG. The protective colloid aqueous solution is stirred and mixed by a stirrer 3 having a blur attached to a rotating shaft.A silver salt aqueous solution, a halogen salt aqueous solution, and a protective colloid aqueous solution are added to a mixer 7 of a reaction vessel, respectively.4.5 and 6. It will be introduced at (At this time, the protective colloid aqueous solution is
These solutions may be added mixed with the aqueous halogen salt solution and/or the aqueous silver salt solution.) These solutions are rapidly and intensively mixed in a mixer and immediately introduced into the reaction vessel 1 via the transport system 8. FIG. 2 shows details of the mixer 7. This mixer 7 has a reaction chamber 1o provided therein, and the reaction chamber 10
A stirring blade 9 attached to a rotating shaft 11 is provided inside.

A silver salt aqueous solution, a halogen salt aqueous solution, and a protective colloid aqueous solution are added to the reaction chamber 1o through three inlets (4, 5, the other inlet is omitted from the drawing), and are rotated at high speed through a zero-rotation shaft ( 1000 r, p, s or more, preferably 2000 r, p, 1 or more, more preferably 30
00r, p, +g or more), the solution containing the fine particles generated by rapid and strong mixing is immediately discharged from the outlet 8 to the outside.

In this way, the ultrafine particles generated by the reaction in the mixer are introduced into the reaction vessel, and because the particle size is fine,
It dissolves in the container and becomes silver ions and halogen ions again, causing uniform particle growth.

The halide composition of these ultrafine particles is kept the same as that of the target silver halide grains.8 The ultrafine particles introduced into the reaction vessel are dispersed within the reaction vessel by stirring inside the reaction vessel. , and from individual fine particles,
Halogen ions and silver ions of the desired halide composition are released. The particles generated in the mixer are extremely fine, and the number of particles is very large. From such a large number of particles, each silver ion and halogen ion (in the case of mixed crystal growth, the target halogen ion) ) is released and occurs throughout the protective colloid in the reaction vessel, allowing quite uniform nucleation and/or particle growth to occur. It is important that silver ions and halogen ions, as aqueous solutions, are never added to the reaction vessel except for PAg adjustment, and that the protective colloid solution in the reaction vessel is not circulated to the mixer. This method is completely different from conventional methods, and can produce surprising effects in the uniform growth of silver halide grains.

In the above particle forming method system, the present invention provides an aqueous solution of a water-soluble halide introduced into a mixer where extremely fine particles are generated, and the halide ions contained in the aqueous solution are chloride ions, It is characterized by being composed of at least two types of bromide ions and iodide ions, and including a step of continuously changing the ratio of the amounts of the two types of halide ions added over time, without making any concessions.

As a specific method for implementing the above, an example of a system as shown in FIG. 4 or FIG. 5 may be used, for example.

In FIG. 4, tanks 41 to 45 are tanks for aqueous solution added to the mixer on the third day, and flowmeters 31, 32, 33, 3
Pump controlled by 4.35 26.27.28.2
The liquid was sent by 9.30.

The ultrafine silver halide grains prepared in the mixer 38 are
It is immediately introduced into the reaction vessel 4o. Stirrers 24 and 25 are installed for the purpose of stirring the inside of the mixer and reaction vessel, respectively. The present invention can be carried out by supplying a silver salt aqueous solution from 42, a protective colloid aqueous solution from 41, and supplying a halogen salt aqueous solution having a different composition from 44.45, and varying the amounts added. A liquid for adjusting the concentration of protective colloid and additive chemicals such as transition metal salts can be supplied from the reserve tank 43 as necessary. Mixing tanks 36, 37 are facilities for mixing the two liquids before each addition to mixer 38. Tank 43 can also be used to supply aqueous halogen salt solutions of different compositions. 43 in this way, or 44.4
By increasing the additive system having the same function in parallel with 5,
Three types of aqueous halogen salt solutions having different compositions can be supplied. Alternatively, if the tank 43 is used to supply the halogen salt aqueous solution, two types of halogen salt aqueous solutions with different compositions can be supplied without using the tank 45.Furthermore, the halogen salt and the protective colloid can be dissolved in the same solution. By supplying from 41 and 43, the present invention can be practiced without using 44 and 45.

The method shown in Figure 5 involves first forming more easily soluble, extremely fine silver halide grains through the reaction of a silver salt aqueous solution with an aqueous halide solution that forms more easily soluble silver halide, and then forming even more easily soluble silver halide grains. The method of carrying out the invention involves the addition of an aqueous solution of a halide salt to form a silver halide for partial conversion. In FIG. 5(a), a halogen salt aqueous solution forming a more easily soluble silver halide is supplied from a tank X1, and a halogen salt aqueous solution forming a less soluble silver halide is supplied from a tank X2. A protective colloid aqueous solution is supplied from a tank 53, and a silver salt aqueous solution is supplied from a tank 54. Each liquid is added to a mixer 63 by pumps 55 to 58 controlled by flowmeters 59 to 62, and the resulting extremely fine silver halide particles are added to a reaction vessel 64. Stirrer 65.6
6 is installed for the purpose of mixing a mixer and a reaction container, respectively. FIGS. 5(b) to 5(d) relate to mixers that can be used in place of the mixer 63, and all of them are arranged so that addition from X2 can occur later. The present invention can be carried out by changing the composition of the silver halide grains supplied to the reaction vessel 64 by continuously changing the degree of conversion by changing the amount supplied from X2.

The fine particles formed in the mixer have very high solubility due to their fine particle size, and when added to the reaction vessel, they dissolve and become silver ions and halogen ions again, forming nuclei or starting a reaction. They deposit on particles already in the container and cause particle growth, but at that time, due to the high solubility of the fine particles, so-called Ostwald ripening occurs among the fine particles in the mixer, causing the particle size to increase. As they grow larger, their solubility decreases, their dissolution in the reaction vessel slows down, and the rate of particle growth is significantly reduced, in some cases no longer dissolving (or, conversely, becoming nucleated by themselves). This causes growth.

In the present invention, this problem was solved by the following three techniques.

■ Immediately after forming the microparticles in the mixer, add them to the reaction vessel.

In the present invention, this Ostwald ripening occurs by providing a mixer very close to the reaction vessel and shortening the residence time of the additive liquid in the mixer, thereby immediately adding the generated fine particles to the reaction vessel. I tried not to. Specifically, the residence time t of the liquid added to the mixer is expressed as follows.

a+b+c V: Volume of the reaction chamber of the mixer (d) a: Addition amount of silver nitrate solution (d/-+n) b = Addition amount of halogen salt solution (d/5in) C; Addition amount of protective colloid solution Cd/gull in) In the production method of the present invention, t is 10
The time is at most 5 minutes, preferably at most 5 minutes, more preferably at most 1 minute, even more preferably at most 20 seconds. The fine particles thus obtained in the mixer are immediately added to the reaction vessel without their particle size increasing.

■ Perform powerful and efficient stirring with a mixer.

James (T.
During coalescence ripening, crystals that were previously far apart come into direct contact and coalesce to form larger crystals, resulting in a sudden change in particle size. Both Ostwald ripening and coalescent ripening occur not only after the end of deposition, but also during deposition. "The coalescence ripening described here is particularly likely to occur when the particle size is very small, and is particularly likely to occur if stirring is insufficient, and in extreme cases, it may even create coarse, clumpy particles. 0 In the present invention, as shown in Figure 2, a closed type mixer is used, so the stirring blade in the reaction chamber can be rotated at a high rotational speed, which is not possible with a conventional open type reaction vessel. (In the open type, if the stirring blades are rotated at high speeds, the liquid will be blown away by the centrifugal force, and there will be problems with foaming, making it impractical). Prevents resence ripening,
As a result, fine particles with extremely small particle size can be obtained. In the present invention, the rotation speed of the stirring blade is 1000.
r, p, m or more, preferably 2000 r, p, - or more,
More preferably, it is 3000r,p,- or more.

(2) Injection of the aqueous protective colloid solution into the mixer The coalescence ripening described above can be significantly prevented by the protective colloid of fine silver halide particles.In the present invention, the aqueous protective colloid solution is added to the mixer in the following manner.

(a) Inject the protective colloid aqueous solution alone into a mixer.

The concentration of the protective colloid is 0.2% by weight or more, preferably 0.
．． 5% by weight is good, and the flow rate is at least 20%, preferably at least 50%, more preferably 100% or more of the sum of the flow rates of the silver nitrate solution and the aqueous halide solution.

(b) Impregnating the halogen salt aqueous solution with a protective colloid.

The concentration of the protective colloid is at least 0.2% by weight, preferably at least 0.5% by weight.

(C) Adding a protective colloid to the silver nitrate aqueous solution.

The concentration of the protective colloid is 0.2% by weight or more, preferably 0.
．． It is 5% by weight or more. When gelatin is used, it is better to mix the silver nitrate solution and the protective colloid solution immediately before use, since gelatin silver is made from silver ions and gelatin, and silver colloid is produced by photolysis and thermal decomposition.

Further, the above methods a to C may be used alone or in combination, or three may be used at the same time.

Gelatin is preferably used as the protective colloid in the present invention.

The following polymer compounds other than gelatin having a protective colloid effect on silver halide grains used in the present invention are used.

(a) Polyacrylamide polymer A homopolymer of acrylamide, a copolymer of polyacrylamide and imidized polyacrylamide, a copolymer of acrylamide and methacrylamide.

伽) Aminopolymer (C) Polymer with thioether group US Patent 3
No. 615624, No. 3860428, No. 370656
Polymer having a thioether group shown in No. 4 (b) Polyvinyl alcohol (e) Acrylic acid polymer Acrylic acid homopolymer, acrylic acid ester polymer having an amino group, halogenated acrylic ester polymer (f) Polymer having hydroxyquinoline ( 6)
Cellulose, starch (iii) acetal (i) polyvinylpyrrolidone (0) polystyrene and low molecular weight gelatin are also used in the present invention.

The average molecular weight of gelatin is preferably 30,000 or less, more preferably 10,000 or less.

By using the synthetic protective colloids, natural protective colloids, and low-molecular-weight gelatin that have been shown so far, it is possible to form fine silver halide grains at lower temperatures than when using ordinary gelatin, resulting in smaller grain sizes. Silver halide can be supplied. Regarding the concentration of the protective colloid used, the concentration of the protective colloid added to the mixer is at least 0.2% by weight, preferably at least 1% by weight, more preferably at least 2% by weight. Silver nitrate aqueous solution and/or
Or, when a protective colloid is contained in the halogen salt aqueous solution, its concentration is 0.2% by weight or more, preferably 1% by weight.
The content is more preferably 2% by weight or more.

The temperature of the mixer is 40°C or lower, preferably 35°C or lower, the temperature of the reaction vessel is 50°C or higher, preferably 60″C or higher,
More preferably, the temperature is 70°C or higher.

The grain size of the fine silver halide used in the present invention can be confirmed by placing the grains on a mesh and using a transmission electron microscope, preferably at a magnification of 20,000 to 40,000 times. It is 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.05 μm or less.

In this method, if a silver halide solvent is added to the reaction vessel, a higher dissolution rate of fine particles and a higher growth rate of grains in the reaction vessel can be obtained.

Examples of the halogenated solvent include water-soluble bromides, water-soluble chlorides, thiocyanates, ammonia, thioethers, and thioureas.

For example, thiocyanate (U.S. Pat. No. 2,222°264)
2,448,534, 3,320.069, etc.), ammonia, thioether compounds (for example, U.S. Pat.
3,704,130, 4,297,439, 4,276.347, etc.), thione compounds (for example, JP-A-53-144319, JP-A-53-82408, JP-A-55-77737, etc.) ), amine compounds (e.g., JP-A-54-100717, etc.), thiourea derivatives (e.g., JP-A-55-2982, etc.), imidazoles (e.g., JP-A-54-100717, etc.), substituted mercaptotetrazoles (e.g., JP-A No. 57-202531, etc.).

The halide composition of the emulsion obtained by the present invention may be any of silver iodobromide, silver chlorobromide, silver chloroiodobromide, and silver chloroiodide, and according to the present invention, the microscopic distribution of halide is uniform. Silver halide mixed crystal grains are obtained.

As an example of silver halide emulsion grains having a uniform microscopic distribution, tabular silver iodobromide grains having a silver iodobromide phase will be described here.

The term ``silver wax distribution is microscopically uniform'' here refers to a more microscopic distribution of silver iodobromide grains, which is completely different from the silver iodide distribution that has been handled up to now. As a means of measuring the silver Tatsude distribution in
For example, King (M
, A, King), M, H, Lorret
to), Maternagha (T, J, Maternagha
n) and Berry (F, J.

``Analytical electron microscopy'' by Berry)
Probeless in Basic Principles of Imaging Systems, International Conference on Photographic Science Cologne (K'61n), 1986, describes the topographical results of silver iodide content in silver iodobromide tabular grains. The size of the electron beam irradiation probe used in this research was 50 people, but in reality the electron beam spreads due to the elastic scattering of electrons, and the diameter of the electron beam spot irradiated on the sample surface was approximately 300 mm. Therefore, this method cannot measure more fine-grained silver iodide distribution.

The silver iodide distribution was also measured in JP-A-58-113927 using the same method, but the size of the electron beam spot used was 0. It was 2μ.

Therefore, depending on these measurement methods, more microscopic (10
It is impossible to clarify the silver iodide distribution (local variations on the order of 0 or less).

This microscopic distribution of silver iodide can be seen, for example, in J.F. Hasilton, Photographic Science and Engineering 111, p. 57, 1967, and Takehiko Shiozawa, Photographic Society of Japan, Vol. 35, No.
It can be observed by a direct method using a low-temperature transmission electron microscope as described in P. 972, p. 213. In other words, the silver halide grains were taken out under safe light to prevent the emulsion grains from printing out, and placed on a mesh for electron microscopy to prevent damage (printout, etc.) from the electron beam.
Observation is performed using the transmission method while the sample is cooled with liquid nitrogen or liquid helium to prevent this.

The higher the accelerating voltage of the electron microscope, the clearer the transmitted image can be obtained.
volt, 1000 for larger particle thicknesses
1 [volt is better. The higher the acceleration voltage, the greater the damage to particles caused by the irradiated electron beam. Therefore, it is preferable to cool the sample with liquid helium rather than liquid nitrogen.

The imaging magnification can be changed as appropriate depending on the particle size of the sample, but is from 20,000 times to 40,000 times.

When a transmission electron micrograph of silver iodobromide tabular grains is taken in this manner, a very fine annual ring-like striped pattern is observed in the silver iodobromide phase.

An example of this is shown in FIG. The tabular grains shown here are
A silver bromide tabular grain is used as a core, and a shell of silver iodobromide containing 1110 mol% iodide is formed outside the core, and its structure can be clearly seen in this transmission electron micrograph. In other words, since the core part is silver bromide and is naturally uniform, only a uniform flat image can be obtained. The pattern can be clearly seen. The spacing of this striped pattern is very small (on the order of 100 people to less than that), indicating very microscopic non-uniformity. Although the heterogeneity can be revealed by various methods, a more direct method is to anneal the tabular grains under conditions that allow iodide ions to move within the silver halide crystal.
This can be clearly concluded from the fact that this striped pattern completely disappears when the temperature is L/ (for example, 250° C. for 3 hours).

The tree-ring-like striped pattern indicating the non-uniformity of silver iodide distribution in the tabular silver iodobromide emulsion grains described here is the same as that cited earlier.
It is clearly observed in the transmission electron micrograph attached to JP-A-58-113927, and is also clearly shown in the transmission electron micrograph in the study by King et al. cited above. Due to these facts, silver iodobromide grains that have been prepared with a constant silver iodide content to obtain a uniform silver iodide distribution have very microscopic particles, which is completely contrary to the intention of their manufacture. It has a non-uniform distribution of silver iodide,
The technology to make it uniform was first disclosed in Japanese Patent Application Laid-Open No. 1183644, Japanese Patent Application No. 194861/1986, etc. The present invention further improves the perfection of silver halide grains using this new grain formation method. This paper discloses a method for increasing

As can be seen from the above description, the particles of the present invention can be obtained by observing a transmission image of the particles using a means for analyzing halogen distribution on a slightly larger scale, such as a molecular electron microscope, and a cooling transmission electron microscope. By doing so, they can be clearly distinguished from conventional silver halide grains. That is, the silver halide grains containing silver iodobromide with a continuously changing silver iodide content prepared according to the present invention include silver iodobromide grains with a continuously changing silver iodide content as determined by an analytical electron microscope. There is a microscopic line due to microscopic non-uniformity of silver iodide in the area of 0. The lines constituting the tree-ring-like striped pattern showing the microscopic heterogeneity of silver iodide, which are present at most two, preferably one, and more preferably none, at intervals of 2 μm, are in the direction of grain growth. They occur in orthogonal fashion, resulting in these lines being distributed concentrically from the center of the particle.

For example, in the case of the tabular grain shown in Fig. 3, the lines constituting the tree-ring-like striped pattern indicating non-uniformity of silver iodide are perpendicular to the growth direction of the tabular grain, and as a result, they are parallel to the edge of the grain. , and the direction perpendicular to these points toward the center of the particle, and is distributed concentrically around the center of the particle.

In the silver halide grains of the present invention, the silver iodide content may be abruptly changed in the partial structure if necessary, but such a boundary line can be determined by the above-mentioned observation method. However, this change in silver iodide content only constitutes a single line, and is clearly not composed of multiple lines resulting from microscopic heterogeneity of silver iodide. Can be distinguished. Furthermore, the line resulting from such a change in silver iodide content can be clearly confirmed by measuring the silver iodide content on both sides of this line using the analytical electron microscope described above. Such a line due to a change in silver iodide content is completely different from a line resulting from microscopic non-uniformity of silver iodide as referred to in the present invention, and indicates a ``macroscopic silver iodide distribution J''.

Furthermore, if the silver iodide content is changed substantially continuously during grain growth, there will be no rapid change in the silver iodide content, so the above-mentioned method will not change regardless of whether or not the method of the present invention is used. No lines indicating macroscopic changes in silver iodide content are observed. Therefore, if there are at least three lines at 0.1 μm intervals, this indicates microscopic non-uniformity in silver iodide content. Therefore, it can be seen that the method of the present invention is not applied.

However, the observation of microscopic non-uniformity in halogen distribution using the above-mentioned cooled transmission electron microscope is strongly influenced by the thickness of the silver halide grains used as the sample, as described above. Requires extreme caution.

As described above, the silver halide grains of the present invention are grains prepared by the method described above, in which the halogen composition changes continuously and there is no microscopic non-uniformity in the halogen distribution in that region. be.

Conventionally known methods can also be applied to the partial structure of the silver halide grains of the present invention, if necessary.

That is, in preparing the photosensitive silver halide grains of the present invention, the entire grain may be prepared by the method of the present invention, or the method of the present invention may be applied as part of the grain preparation, and the rest may be prepared by conventional known methods. For example, the core and shell of a core-shell type particle in which the interior and surface layers of the particle have different halogen compositions are each prepared by a known method, and only the region between the core and shell with different halogen compositions is treated according to the present invention. Alternatively, the present invention may be applied to the preparation of the core or shell and the halogen composition of each may be varied, or the particle formation method system used in the practice of the present invention may be used to prepare a constant halogen composition. It is also preferable to incorporate a partial structure into the silver halide grains of the present invention. Similarly, in the preparation of epitaxial particles, the host may be prepared by a known method and the method of the present invention may be applied to the guest preparation.

Further, by adding fine-sized silver halide grains prepared into the reaction vessel using the grain formation method system used for carrying out the present invention, grain nuclei are formed in the reaction vessel, and Crystals can be grown.

It is also possible to grow crystals by forming grain nuclei in the reaction vessel by a conventionally known method and adding the fine silver halide particles described above.

Regarding the known particle formation method used as described above, see "Physics and Chemistry of Photography" by Glafkides, published by Paul Montell (P., Glafkides, Chimie et al.
Physique Photographique P
aul Montel+ 1967), by Duffin
'Photographic Emulsion Chemistry', published by Focal Press (G, F, Du
ffin, Photographic Es+uls
ion Chemist-ry (Focal Pre
ss, 1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V., L., Zeli.
ke+an at al, Making and C
makingPhotographic Esulsio
n+ Focal pre3g+ (1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. A method in which zero particles are formed in an excess of silver ions (so-called back mixing method) can also be used. As one type of simultaneous mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

In addition to the above methods, the following method disclosed in JP-A-1-183644 can also be used. That is,
Nucleation and/or grain growth also occurs in the zero method, which is a method in which a fine-grain silver halide emulsion having fine-sized grains prepared in advance is added to a reaction vessel to cause nucleation and/or grain growth. No aqueous solution of a water-soluble silver salt or aqueous solution of a water-soluble halide is added to the reaction vessel except for the purpose of determining the pAgm of the emulsion in the reaction vessel.Prior to adding this pre-prepared emulsion to the reaction vessel,
In this method, the grain formation temperature of the fine grain emulsion prepared in advance is 4.
The temperature of the reaction vessel to which the fine grain emulsion is added is 50°C or higher, preferably 60°C or higher, and more preferably 70°C or higher.

Furthermore, in the present invention, the concentration of the protective colloid aqueous solution in the reaction vessel when preparing the fine grain emulsion in advance is 0.2% by weight or more, preferably 1% by weight or more, and more preferably 2% by weight or more.

The silver halide emulsion of the present invention has a distribution or structure regarding the halogen composition in its grains. There are various patents regarding silver halide emulsions prepared by conventional grain forming methods, but the typical one is
3-13162, JP-A No. 61215540, JP-A-60-222845, JP-A-61-75337, etc., the core-shell type or double-layer particles have different halogen compositions in the inside and surface layers. It is a structured particle. In such particles, the shape of the core portion and the overall shape including the shell may be the same or different. Specifically, the core part has a cubic shape, and the shape of the shelled particle may be cubic or octahedral. Conversely, the core may be octahedral and the shelled particle may be cubic or octahedral.

Although the mako core part is a clearly regular particle, the shelled particle may have a distorted shape or an irregular shape. Moreover, it is not just a double structure, but also JP-A-60-2
It is possible to form a triple structure as disclosed in No. 22844 or a multilayer structure, or to apply a thin layer of silver halide having a different composition to the surface of a core-shell double structure grain.

In order to give a structure to the inside of a particle, it is possible to create a particle having not only the above-mentioned enveloping structure but also a so-called bonding structure. These examples are disclosed in Japanese Patent Application Laid-Open No. 51-13354.
No. 0, Japanese Patent Publication No. 58-108526, EP199290
A2, JP 5824772, JP 59-1625
It is disclosed in No. 4, etc. The crystal to be bonded can have a composition different from that of the host crystal and can be formed by bonding to an edge, part of a corner, or surface of the host crystal. Such a bonded crystal can be formed even if the host crystal is uniform in terms of halogen composition or has a core-shell structure. In the case of a bonded structure, a combination of silver halides is naturally possible, but a bonded structure can be obtained by combining a silver halide with a silver salt compound that does not have a rock salt structure, such as silver rhodan or silver carbonate. Further, non-silver salt compounds such as pbo may also be used if a bonded structure is possible.

In the case of silver iodobromide grains having these structures, for example, in a core-shell type grain, even if the core part has a high silver iodide content and the shell part has a low silver iodide content, or conversely, the core part has a low silver iodide content. The particles may have a low silveride content and a high shell portion. Similarly, grains having a bonded structure may be grains in which the host crystal has a high silver iodide content and the bonded crystal has a relatively low silver iodide content, or vice versa.

These particles with different halogen compositions have individual differences in photographically important factors such as light absorption, adsorption of adsorbed additives, suitability for chemical sensitization, latent image formation efficiency, and developability, compared to particles with a constant composition. However, by applying the present invention to the preparation of these particles, the performance can be further improved. The mechanism is complex and can vary, but when the particles described above are prepared using conventional methods, lattice defects are introduced, as represented by the lines observed with the aforementioned cooled transmission electron microscope, which can be seen in the photograph. This is thought to be because it has a harmful effect on the body.

The silver halide grains used in the present invention may be normal crystals that do not contain twin planes; For example, choose from single twins with one twin plane, parallel multiple twins with two or more parallel twin planes, nonparallel multiple twins with two or more nonparallel twin planes, etc. depending on your purpose. It can be used in In the case of normal crystals, it is a cube consisting of (100) planes, an octahedron consisting of (111) planes, and
Octahedral particles consisting of (110) planes disclosed in No. 42737 and JP-A No. 60-222842 can be used. Furthermore, Journal of Imaging
5science Vol. 30, page 247, as reported in 1986 (211) is a representative example (hl)
Mentako, (331) is a representative (hhl) Mentako, (
(n k O) surface roughness representing the surface (210) and (321
) surface roughness (nkl), which is representative of the surface (nkl), can also be selected and used depending on the purpose, although the preparation method requires some ingenuity. (10
Tedecahedral particles in which 0) planes and (111) planes coexist in -ku particles, particles in which (100) planes and (110) planes coexist, or particles in which (111) planes and (110) planes coexist, etc.
Particles in which two surfaces or many surfaces coexist can also be selected and used depending on the purpose.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling PAg and pH during grain formation. For more information, please see Photographic Science
and Engineering (Photographic
5science and engineering)
Volume 6, pp. 159-165 (1962); Journal of Photographic Science (Journa
lof Photography 5science)
, Vol. 12, pp. 242-251 (1964), U.S. Patent No. 3,655°394 and British Patent No. 1.41.
3.748.

Further, tabular grains having an aspect ratio of 3 or more can also be used in the present invention. Tabular grains are described in ``Theory and Practice of Photography'' by Creep, Photogra
phyTheory and Practice (1
930), p. 131; Gatoff, Photographic Science and Engineering (Cuto
ff, Photographic Science a
nd Engineering), Volume 14, 248~
257 pages (1970); US patent cylinder 4,434°22
No. 6, No. 4,414,310, No. 4.433.048
No. 4,439,520 and British Patent No. 2,11
It can be easily prepared by the method described in, for example, No. 2,157. When tabular grains are used, there are advantages such as increased covering power and increased color sensitization efficiency with sensitizing dyes, as disclosed in the above-cited U.S. Patent No. 4,434,226.
As the emulsion of the present invention, tabular grains are preferred, and tabular grains in which grains with an aspect ratio of 3 to 8 account for 50% or more of the total projected area are particularly preferred.

The silver halide emulsion used in the present invention is EP-009672.
781, BP-0064412B1, or DE-2.
306447C2, surface modification as disclosed in JP-A No. 60-221320 may also be carried out.

The silver halide emulsion used in the present invention is preferably a surface latent image type emulsion, but an internal latent image type emulsion may also be used by selecting the developer or development conditions as disclosed in JP-A-59-133542. I can do it. In addition, a shallow internal latent image type emulsion overlaid with a thin shell can also be used depending on the purpose.

The grain size of the obtained silver halide may be fine grains of 0.1 micron or less, large grains with a projected area diameter of up to 10 microns, or a monodispersed emulsion with a narrow distribution.
Alternatively, a polydisperse emulsion having a wide distribution may be used.

A so-called monodisperse silver halide emulsion having a narrow grain size distribution in which 80% or more of all grains fall within ±30% of the average grain size in terms of grain number or weight can be used in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are mixed in the same layer or in separate layers in emulsion layers having substantially the same color sensitivity. Can be applied in multiple layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

In the present invention, it is extremely important to perform chemical aggravation typified by reduction sensitization, sulfur sensitization, and gold sensitization. Reduction aggravation can be effectively carried out according to International Publication R (WO) 89-06831 and its cited documents. The location where chemical sensitization is applied varies depending on the composition, structure, and shape of the emulsion grains, as well as the intended use for which the emulsion will be used. When chemically sensitizing nuclei are embedded inside grains, they should be embedded shallowly from the grain surface. Although the effect of the present invention is effective in any case where chemical sensitizing nuclei are formed in the vicinity of the surface, it is particularly preferable when chemical sensitizing nuclei are formed near the surface. In other words, surface latent image type emulsions are more effective than internal latent image type emulsions.

Chemical sensitization is described in James (T. H. James, The Photographic Process, 4th edition, Macmillan Publishing, 1977).
e Theory of the Photography
ic Process, 4th de, Macmi
llan 1977), pages 67-76, or as described in Research Disclosure, Vol. 120, April 1974, 1.
2008F Research Disclosure Volume 34, 1
June 975, 13452, U.S. Patent No. 2,642,3
No. 61, 3,297°446, 3,772.03
No. 1, No. 3,857.711, No. 3,901,714
No. 4゜266.018 and No. 3,904.41
pAg 5-10, pH 5-8 and temperature 30-10 as described in No. 5 and British Patent No. 1,315.755.
It can be carried out at 80° C. using sulfur, selenium, tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers.

Chemical sensitization is optimally carried out in the presence of gold compounds and thiocyanate compounds and as described in U.S. Pat.
, 266.018 and 4.054.457, or in the presence of sulfur-containing compounds such as hypo, thiourea compounds, and rhodanine compounds. Chemical sensitization can also be carried out in the presence of chemical sensitization aids.

The chemical sensitizing aid used is a compound known to suppress fog and increase sensitivity during the process of chemical sensitization, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers include U.S. Pat. Nos. 2,131,038 and 3,411,914;
3.554757, JP-A-58-126526, and the aforementioned author Duffin [Photographic Emulsion Chemistry, pp. 1138-143].

When chemical sensitization using gold salt is performed, the formation of fog due to the reaction between reduced silver nuclei and gold salt is prevented by adding the oxidizing agent and/or inhibitor prior to grain formation in the region. For example, when a gold salt is used in chemical sensitization of the particle surface, it is preferable that particle formation in a region of at least 0.001 μm from the particle surface is carried out in the presence of an inhibitor.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; There are many known antifoggants or stabilizers such as zaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,?) tetraazaindenes), pentaazaindenes, etc. Compounds can be added. For example, U.S. Patent No. 3,95
No. 4,474, No. 3゜982゜947, Special Publication No. 1972-
28.660 can be used.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and others. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the basic heterocyclic nuclei commonly used for cyanine dyes can be applied to these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus,
Selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., indolenine nucleus, benz Indolenine nucleus, indole nucleus, benzoxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Representative examples are U.S. Pat. No. 2,688,545;
No. 977.229, No. 3,397,060, No. 3,5
No. 22,052, No. 3,527,641, No. 3,61
No. 7,293, No. 3,628゜964, No. 3,616
, No. 480, No. 3,672.898, No. 3,679.
No. 428, No. 3゜703.377, No. 3,769.3
No. 01, No. 3 814.609, No. 3,837,86
No. 2, No. 4,026,707, British Patent No. 1,344
No. ゜281, No. 1,507.803, Special Publication No. 4349
No. 36, No. 53-12,375, JP-A No. 52-110
, No. 618 and No. 52-109,925.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

The dye may be added to the emulsion at any stage of emulsion preparation that has been known to be useful.
Most commonly, this is done after chemical sensitization is completed and before application, but as described in U.S. Pat. Nos. 3,628,969 and 4,225,666, Spectral sensitization can be carried out simultaneously with chemical sensitization by adding at the same time, or it can be carried out prior to chemical sensitization as described in JP-A-58-113,928. It is also possible to start spectral sensitization by adding it before the completion of precipitation formation. Furthermore, U.S. Patent No. 4.22
Adding these said compounds separately as taught in No. 5.666, i.e. some of these compounds are added before chemical sensitization and the rest after chemical sensitization. is also possible, as described in U.S. Pat. No. 4,183,756.
Any time during the formation of silver halide grains may be used, including the method taught in No.

The amount added is 4X10-' to 8 per mole of silver halide.
X10-'' moles can be used, but in the case of a more preferable silver halide grain size of 0.2 to 1.2 μm, about 5
X10-' to 2X10-3 moles are more effective.

The various additives described above are used in the photosensitive material related to the present technology, but various other additives can also be used depending on the purpose.

These additives are described in more detail in Research Disclosure+ Item 17643 (1978.1).
(February) and Item I 8716 (November 1979), and the relevant sections are summarized in the table below.

Additive type l Chemical sensitizer 2 Sensitivity increaser Brightener OR/7643 OR/8716 Page 23 Page 648 Right column Same as above Page 24 Ultraviolet absorber Anti-stain agent Dye image stabilizer Hardener Binder Plasticizer, lubricant 25 Page right column Page 25 Page 26 Page 26 Page 27 Page 650 Page left to right column Page 651 Left column Same as above Page 650 Right column Surfactant 13 Static inhibitor Page 27 Same as above In addition, in the photographic emulsion layer of the photographic light-sensitive material of the present invention. may contain a photographic emulsion not produced by the production method of the present invention.

(Example) Example 1 A silver chlorobromide emulsion before chemical sensitization was prepared as follows.

■-A Comparative Example> As shown in Figure 1, 100 ml of
A 3:1M aqueous solution containing 6.0kg of silver nitrate per minute! (
1), an aqueous solution containing 2.52 kg of potassium bromide and 1.86 kg of sodium chloride 321 (II) and 5% by weight
Low molecular weight gelatin (average molecular weight 20,000) aqueous solution 32i!
was added by triple jet. Ultrafine particles (average size of about 0.02 μm) generated by stirring and reaction in the mixer were immediately and continuously introduced into the reaction vessel from the mixer. During this time, the temperature of the mixer was kept at 20°C, and the speed was 2000 rps.
280g of NaC was added to the 0 reaction vessel that had been stirred.
1,1,3Hs HI was dissolved in 361 distilled water in advance and stirred while keeping the temperature at 75°C. 6. An aqueous solution containing 1.2 kg of silver nitrate over a period of 20 minutes. 4I! , (I[I) and 756g
of potassium bromide and 248 g of sodium chloride6. 41 (fV) and 5% by weight aqueous solution of low molecular weight gelatin6. , iI! was added to the mixer using a triple jet to obtain ultrafine particles, which were continuously introduced into the reaction vessel immediately after generation. 5 minutes after the addition was complete, the temperature was lowered to 30°C.
It was desalted using a conventional method. Add water and gelatin, pH 6.5
0, pAg 7.80, average particle size 1.2
A cubic emulsion (1-A) with an outer high silver bromide structure and an average silver bromide content of 65% was obtained.

1-B <This invention> Aqueous solution containing 5.04 kg of potassium bromide 38°41 (
V) and 5.05 kg of sodium chloride in an aqueous solution 38
．． A silver chlorobromide cubic grain emulsion (+-B) was prepared by preparing each of 41 (Vl) separately and mixing the two halogen salt aqueous solutions immediately before adding them to a mixer.

7. Aqueous solution containing 2 kg of silver nitrate 38.44! (■)
38.14 of a 5% by weight aqueous low molecular weight gelatin solution and two aqueous halogen salt solutions were each added to the mixer for 120 minutes to obtain ultrafine particles, which were immediately introduced continuously into the reaction vessel after being produced. For the first 80 minutes, add 192cc of (V) solution/
(Vl) solution was added at an addition rate of 141 cc/min,
Minutes after the start of addition (80 x t≦120),
) liquid ((t-80)X2.4+1921cc/min, (Vl)
Solution (141-(t-8o)xl, average grain size 1.2 μm was produced in the same manner as in Emulsion 1-A, except that 0 or more was added at an addition rate of 1671 cc/min.

A cubic emulsion (1-B) having an outer high silver bromide structure with a continuously changing composition structure and an average silver bromide content of 65% was obtained.

Comparative Example> Halogen salt aqueous solution (If
) is composed of 1.26 kg of potassium bromide and 2°48 kg of potassium bromide.
Cubes with an outer high silver bromide double structure having an average particle size of 1.3 μm and an average silver bromide content of 40% were prepared in the same manner as in (1-A) except that the aqueous solution containing sodium chloride was changed to 28.51 (■). An emulsion (■-C) was obtained.

-D <This invention> In the preparation of emulsion (1-B), the addition rate of liquid (V) and liquid (Vl) was set at 96 cc/l for the first 80 minutes.
(Vl) liquid at 189 cc/min, and after the start of addition (80<t≦120), (V) liquid ((t-8
0)X4.8+96)cc/min, (Vl) liquid (189-
(t-80)
A cubic emulsion (1-D) having a continuous compositional change structure with an outer high silver bromide structure and an average silver bromide content of 40% was obtained.

For the above unchemically sensitized emulsions (1-A) to (1-D),
Ribonucleic acid (manufactured by Sanyo Kokusaku Valve Co., Ltd.: trade name RNA-F) 1
Chemical sensitization was carried out with triethylthiourea at pH 8.0 in the presence of 20 μm/1 mole of Ag. The temperature was 50° C., and the time was selected at the point where the highest sensitivity was obtained under each condition.

The above four types of chemically sensitized emulsions were coated on a cellulose triacetate base in such a manner that the coated silver amount was 3.5 g/rrf and the coated gelatin amount was 5 g/n.

1 with white light at a color temperature of 5400 through a continuous wedge.
/100 seconds of exposure was applied, and the following development process was performed. The photographic density was measured with a densitometer and the results shown in Table 1 were obtained.

Process temperature 20°C 20°C 20'C Time 3 minutes 5 minutes as shown in Table 1 Developing and fixing Water application Washing developer Hydroquinone p-methylaminophenol borax Add anhydrous sodium sulfite water g g 1, 97 g 00 g 1 Fixer Sodium thiosulfate 300g Anhydrous sodium sulfite 15g Glacial acetic acid
Add 12g water
11 In Table 1, the sensitivity is expressed as the reciprocal of the exposure amount that gives an optical density 0.1 higher than the Capri density, and is expressed as a relative value with the sensitivity of sample 101 developed for 5 minutes as 100. The gradation was expressed as the difference in the logarithm of the exposure amount that gives optical densities 0.1 and 0.6 degrees higher than the Capri density, respectively.

From the results shown in Table 1, the light-sensitive materials using the emulsions obtained by the method of the present invention had favorable results of high sensitivity and hard gradations at all development times. Furthermore, changes in sensitivity and gradation due to fluctuations in development time are smaller than those of the comparative examples, and stable photographic properties are exhibited, which is preferable for practical use.

Example 2 A multilayer color print sample having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. At this time, by changing the emulsion used in the -th layer, Samples 201 to 2
04 was produced.

I Structure The composition of each layer is shown below. The numbers represent the coating amount (g/po); however, for silver halide emulsions, the coating amount is in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiCh) and a bluish dye (ulmarine blue)] -th layer (pre-malignant silver halide emulsion layer) Spectral sensitizer (Sen-1) Monodisperse silver chlorobromide emulsion (EM-1) with the addition of 0.09 Monodisperse silver chlorobromide emulsion with the addition of a spectral sensitizer (Sen-1) (Table 2) 0.21 Anticapri agent (Cpd) -1) 0.004 gelatin
1.28 yellow coupler (E
x Y) 0.68 anti-capri agent (CPd-
2) 0.006 color image stabilizer (Cpd-3)
, 0.07 solvent (Solv-1 and 5olv-2 volume ratio 1:1) 0.24 second layer (
Color mixture prevention layer) Gelatin 1.34 Color mixture prevention agent (Cpd-4) °0.04 Solvent (Solv
-3 and 5olv-4 volume ratio 1:1) 0.02 third layer (
Green-sensitive silver halide emulsion layer) Monodisperse silver chlorobromide emulsion (EM-2) with added spectral sensitizer (Sen-2, 3) 0.125 anti-capri agent (Cpd-1) Anti-capri agent (Cpd -5) Gelatin magenta coupler (ExM) Color image stabilizer (Cpd-6) Color image stabilizer (Cpd-7) Color image stabilizer (Cpd-8) Color image stabilizer (Cpd-9) Solvent (Solv-3 and 5olv-5 Volume ratio 1:2) Fourth layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (UV-1/2/3 molar ratio 1:4:4) Color mixing inhibitor (Cpd-4) Solvent (Solv- 6) Fifth layer (red-sensitive silver halide emulsion layer) Monodisperse silver chlorobromide emulsion (EM-3) added with a spectral sensitizer (Sen-4, 5) 0.002 0.001 1,47 0 , 32 0, 10 0.0B 0, 03 0.004 0, 65 1, 43 0, 47 0, 05 0, 24 0, 20 0, 06 Monomer added with spectral sensitizer (Sen-4, 5) Dispersed silver chlorobromide emulsion (EM-4) Anti-capri agent (Cpd-2) Anti-capri agent (Cpd-10) Anti-capri agent (Cpd-11) Gelatin cyan coupler (ExC-1) Cyan coupler (ExC-2) Color image stabilizer (UV-1/3/4 molar ratio 1ll) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-7) Color image stabilizer (Cpd-8) Solvent (Solv 1) Sixth Layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (UV-1/2/3 molar ratio 1:4:4) Solvent (Solv-5) 0, 14 0.00B 0.0001 0.0001 0, 85 0, 13 0,15 0.067 0,25 0.004 0,00? 0,16 0,38 0,13 0,06 Seventh layer (protective layer) Gelatin 1.25 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.05 Liquid paraffin 0.02 Used in the above sample Details of the silver halide emulsions are shown in Table 3.

(Sen-1) (Sen-2) 3゜ 2゜ 8X10-' mol/Ag mol lXl0-' mol/Ag mol Coefficient of variation = standard deviation / average particle diameter (Sen-3) 4゜ 2X10-' mol/Ag mol (CHt)450! − (Sen 4) 6° 1×10 5 mol/Ag mol (Sen 5) 2゜ 3×10 Gomol/Agmol (ExC-1) (ExC 2) 2 (Cpd 1) (cpa 2) (E x Y) (ExM) L hH13 No. 1: 1 mixture (molar ratio) (cpd 3) -(-CHz-CH+r- CONHC.

Hq(t) molecular weight Approximately 60° 00 (Cpd 4) (cpa 5) (Cpd 6) (cpa 7) (cpa 8) (Cpd 9) Color image stabilizer (UV-3) (UV 4) (Solv-1) (Solv 2) -P (OC9 )1. , (iso))s (Solv 3) (Cpd-10) (Cpd-11) (UV-1) (UV-2) (Solv-4) (Solv-5) C: 5 O-P-(-OCR.

HC4 H9).

(Solv-6) C00CH.

HC4 H9 z s As a gelatin hardening agent for each layer, 1-oxy- 3゜ 5-dichloro-5-) riazine sodium salt was used.

Furthermore, the following two types of dyes were used as irradiation-preventing dyes.

And based on the above layer structure, the emulsion of the -th layer was prepared in Example-1.
Samples 201 to 204 were prepared using different emulsions.

A photosensitive needle (F manufactured by Fuji Photo Film Co., Ltd.) is attached to the above photosensitive material.
Gradation exposure for sensitometry was applied through a three-color separation filter using a WH type (light source color temperature: 3200 K).

The exposure at this time was carried out so that the exposure time was 0.1 seconds and the exposure amount was 250 CMS. After exposure, the following processing steps were performed.

[Processing process] [Temperature] [Time] Color phenomenon 33°C 3 minutes 30 seconds Bleach fixing 33
■ Rinsing at 30-34°C for 60 seconds ■ Rinsing at 30-34°C for 60 seconds ■ Drying at 30-34°C for 60 seconds Drying at 70-80°C for 50 seconds (washing ■ → ■ ) The composition of each treatment liquid is as follows.

Sadate Niri 1 liquid water 800
d Diethylenetriamine” Pentaacetic acid 1.0 g Nitrilotriacetic acid 1.5 g Benzyl alcohol 15 d Diethylene glycol 10 d Sodium sulfite
2.0g potassium bromide
0.5g potassium carbonate 30g
N-Ethyl-N-(β-methanesulfonamidoethyl)-3 Monomethyl-4-aminoaniline, sulfate hydroxylamine, sulfate optical brightener (WHITEX 4B, manufactured by Sumitomo Chemical ■) Add water and adjust the pH (at 25℃) ) In! 1 Ammonium thiosulfate (70%) Sodium sulfate Iron ethylenediaminetetraacetate (nl) Ammonium ethylenediaminetetraacetic acid disodium 5.0g 4.0g 000d 10.20 Table 2 shows the measurement results of the yellow image measured with a blue filter. However, the sensitivity is expressed as the reciprocal of the exposure amount that gives an optical density 1.0 higher than the Capri density, and is expressed as a relative value with the sensitivity of Sample 201 as 100.

The gradations are 1.0 and 0.0, respectively, based on Capri density. 2 It is expressed as the difference in the logarithm of the exposure amount that gives a higher optical density.

Table 2 also shows the change in gradation when the developing temperature was changed to 29°C.

Table 2 00d 50d 8g 5g Add water and pH (25°C) 100 (ld 6, 70) As shown in Table 2, the sample according to the present invention has high sensitivity and hard gradation, and furthermore, the gradation due to variations in development conditions. The change in tone is extremely small.

(Example 3) A silver iodobromide emulsion before chemical sensitization was prepared as follows.

Iodine 3-A O, 2°0% by weight containing 126 moles of potassium bromide
While stirring, a 1.2 mol silver nitrate solution and a halogen salt aqueous solution containing 0.9 mol potassium bromide and 0.3 mol potassium iodide were added to 2.6 mol of gelatin solution using the double jet method while stirring. Each 1200 d was added over 15 minutes. During this time, the gelatin solution was kept at 35°C. Thereafter, the emulsion was washed by a conventional noflocculation method, 30 g of gelatin was added and dissolved, and the pH was adjusted to 6.5 and the pAg to 8.6. The obtained silver iodobromide fine particles (silver iodide content 2
5%) had an average particle size of 0.05 μm.

side
-B 0.5% by weight gelatin solution containing 0.05 mol potassium bromide and 1.22% by weight while stirring it.
In a reaction vessel to which 30d of 3.6-cythiaoctane-1.8-diol was added and kept at 75°C, 100g of silver iodobromide fine grain emulsion (3-A) (containing silver equivalent to Log in silver nitrate) and 501d of water were added. The added and dissolved emulsion was added for 10 minutes to perform nucleation. The silver iodobromide octahedral core particles obtained had a diameter of 0°55.

Subsequently, 1000 g of fine grain emulsion (3-A) (containing silver equivalent to 90 g of silver nitrate) was continuously added to the reaction vessel over a period of 60 minutes. After this, the emulsion was cooled to 35°C and
Wash with water using the usual flocculation method and add gelatin 7.
0g was added to adjust the pH to 6.2 and pAg to 8.8. The obtained core emulsion grains had an average projection plane equivalent diameter of an ellipse of 1.2 μm.
It was an octahedral silver iodobromide emulsion (iodide content: 25 mol%).

Yo-ni-C <Comparative example> 400 g of silver iodobromide octahedral core emulsion (3-B) (5
A reaction vessel containing 1.21 g of an aqueous solution containing 0 g of silver) and 0.003 mol of potassium bromide was maintained at 75° C. without stirring.

500 d of a 0.59 mol silver nitrate aqueous solution, 500 d of a 2% gelatin aqueous solution with a potassium bromide concentration of 0.60 mol, and 2N of a 1% gelatin aqueous solution were added to a mixer placed near the reaction vessel over 250 minutes using a triple jet method. . The temperature of the mixer was 20°C, and the rotation speed of the stirring blade was 200.
0r, p, s, the obtained fine particles were 0.02
It was μm.

The fine particles produced in the mixer were continuously introduced into a reaction vessel maintained at 75°C. The obtained silver iodobromide double-structure octahedral emulsion 3-C had a size of 1.5 μm (average silver iodide content 12.5 mol%).

Comparative Example: In the preparation of the silver iodobromide double-structure octahedral emulsion (3-C), the halogen composition of the 2% gelatin aqueous solution added to the mixer installed near the reaction vessel was For .5 minutes, the potassium bromide concentration was 0. 452 mol, potassium iodide concentration is changed to 0.1475 mol, and for the subsequent 187.5 minutes,
As in (3-C), the potassium bromide concentration was set to 0.60 mol, and emulsion 1 was prepared in the same manner as in (3-C), and silver iodobromide double structure emulsion (3-D) was prepared with size 1. It was 5 μm (average silver iodide content 15.6 mol%).

Yo
(3-E) Present invention> In the preparation of the silver iodobromide double-structured octahedral emulsion (3-C), 0.59 mol of odor was added as a 2% gelatin aqueous solution to a mixer installed near the reaction vessel. Separately prepare a solution <E-1> containing potassium iodide and a solution <E-u> containing 0.59 mol of potassium iodide, and immediately before adding the two 2% gelatin to the mixer. A silver iodobromide continuously changing composition octahedral emulsion (3-E) was prepared by mixing aqueous solutions. For the first 125 minutes, minutes after the start of the addition (
The flow rate of solution <E-1> with 0≦t<125) is set to (1,53
+ Punishment) d/min, the flow rate of the solution <E-It> is (0,5
0+-6) d1 minute, and for the remaining 120 minutes,
Emulsion (
A silver iodobromide octahedral emulsion (3-E) (size 1.5 .mu.m, average silver iodide content 15.6 mol %) was obtained in the same manner as 3-C).

In the preparation of Io3-F3-G silver iodobromide octahedral emulsions (3-D) and (3E), after 250 minutes of addition of fine-grained silver halide from a mixer placed next to the reaction vessel. Then, stirring was continued while the reaction vessel was maintained at 75°C, and 50 ml of a 0.59 molar silver nitrate aqueous solution and 5° d of a 0.60 molar potassium bromide aqueous solution were directly added to the reaction vessel by the double jet method (addition Required time: 10 minutes) Silver iodobromide double structure octahedral emulsion (3-F) <Comparative example>, silver iodobromide continuous composition change in the same manner as (3D) and (3-E) except for 0 or more An octahedral emulsion (3-C,) <this invention> was prepared. Each had a size of 1.52 μm and an average silver iodide content of 14.9 mol%.

Emulsions (3-C) to (3-G) obtained as above
Sodium thiosulfate (1,0
XIO-' mol 1 mol Ag), chloroauric acid (1,2X1
0-' mol 1 mol Ag) and potassium thiocyanate (2,
2×10 −'mol 1 mol Ag) was added for optimal chemical sensitization. Thereafter, the compounds shown below were added, and a triacetylcellulose film having an undercoat layer was coated on the support together with a protective layer by coextrusion.

The emulsion at the time of chemical sensitization had a pH of 6 and a 2pAg of 8.7.

(1) Emulsion layer - Emulsion Emulsion shown in Table 4 (coated silver amount 3 g/rrf) - Coupler - Tricresyl phosphate - Stabilizer 4-hydroxy-6-methyl-13,3a,
? -Tetrazaindene Antifoggant 1-(m-sulfophenyl)5-mercaptotetrazole Coating aid Sodium dodecylbenzenesulfonate (2) Protective layer 2,4-dichloro-6-hydroxy-5- ) riazine sodium salt/gelatin 18 to these samples. . A second sensitometric exposure was applied, followed by color development.

The concentration of the treated sample was measured using a green filter.

The photographic performance results obtained are shown in Table 4. The sensitivity is the reciprocal of the exposure amount that gives a density of fog + 0.2, and the 0 gradation is the density at the exposure amount that gives a density of fog + 0.2 and its 1
It was expressed by the difference in density at 0 times the exposure amount. Relative sensitivity was set at 100 for sample 301. The development process used here was carried out at 38°C under the following conditions.

1. Color development 2 minutes 45 seconds 2 Bleaching
6 minutes 30 seconds 3, water washing 3 minutes 15 seconds 4, fixing 6 minutes 30 seconds & water washing 3 minutes 15 seconds 6, stability 3 minutes 15 seconds The composition of the processing solution used in each step is as follows.

Sodium Nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide
1.4g hydroxylamine sulfate 2.4g 4-(N-ethyl-N-βhydroxyethylamino-2-methylaniline sulfate 4.5g water
11Ll-hill ammonium bromide 160.0g aqueous ammonia (28%) 25. (ld ethylenediamine-sodium tetraacetate, add glacial acetic acid water, add sodium tetrapolyphosphate, sodium sulfite, ammonium thiosulfate (70%), add sodium bisulfite water, add formalin water, add 30 g. 4d 1 2,0g 4,0g 175.0d 4,6g 1 8,0g 2 As shown in Table 4 (Sample 3 using the emulsion of the present invention)
03,305 had high sensitivity and hard gradation. The developed sample was observed under magnification and the graininess was compared, and the graininess (compared with the same density) was found to be the same as the sample of the present invention.

Next, in order to investigate changes in photographic properties due to mechanical pressure,
Before exposure for sensitometry of /100 seconds was applied, the coated sample was bent along a cylinder with a diameter of 6 cm, pressure was applied, and changes in density after development were examined. Sample 301 of comparative example
, 302, and 304, a decrease in density was observed in the folded part, especially in the gradation part, but the sample 303.30 of the present invention
In No. 5, this density change was significantly improved.

From the above, it was shown that the present invention provides a silver halide photographic light-sensitive material that has high sensitivity, hard gradation, and shows little change in photographic properties due to mechanical pressure.

Example 4 Emulsions (3-C) to (3-G) of Example 3 were used in a multilayer color light-sensitive material having the following configuration, and their performance was evaluated. The color development process was performed by changing the color development time of Example 3 from 2 minutes 45 seconds to 3 minutes.
The same procedure as in Example 3 was carried out except that the time was changed to minutes and 15 seconds.

on a subbed cellulose triacetate film support.
A sample of a multilayer color photosensitive material is prepared by coating each layer with the composition shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/rrf units. For halogen and silver oxide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount is expressed in g/rrf. The coating amount is shown in moles based on 111 moles of halogenide.

1st layer (Haley silane prevention layer) Black colloid f! it! 1 0
．． 18 gelatin 1.40
2nd layer (middle layer) 2.5-di-t-pentadecylhydroquinone 0.18EX-
10,07 E Dye Sensitive ■ EX-2 EX-10 -1 -2 -3 B5-1 Gelatin 0.002 0.06 0.08 0.10 0.10 0.02 1.04 i 0.25 Silver 0.25 6 .9X10-'1.8X10-' 3, lX10-' 0.335 0.020 0.07 0.05 0.07 0.060 0.87 4th layer (second red milk layer) Emulsion G increase Sensitizing dye Summer sensitizing dye ■ Sensitizing dye ■ EX -'2 EX-3 EX-10 -1 -2 -3 Gelatin 5th layer (third red-sensitive emulsion layer) Emulsion sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-3 EX-4 EX-2 MA 1.0 5, lX10-'1.4X10-'2.3X10-' 0.400 o, os.

O,015 0,07 0,05 0,07 1,30 MA 1.60 5.4X10-'1.4X10-'2.4X10-' 0.010 0.080 0.097 B5-1 B5-2 Gelatin 6th layer (intermediate layer) EX-5 B5-1 Gelatin 7th layer (first green-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-6 EX-1 EX-7 EX-8 B5-1 B5-3 Gelatin 0.22 0.10 1.63 0.040 0.020 0.80 Silver 0.15 Silver 0.15 3, OX 10-'1.0X10-' 3.8X10 -' 0.260 0.021 0.030 0.025 0.100 0.010 0.6J 8th layer (second green emulsion layer) Emulsion C Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ EX- 6 EX-8 EX-7 B5-1 B5-3 Gelatin 9th layer (third green-sensitive emulsion layer) Emulsion E Sensitizing dye V Sensitizing dye■ Enhancing dye■ EX-13 EX-11 EX-1 B5- 1 11 O, 45 2, lX10-'7.0X10-'2.6X10-' 0.094 0.018 0.026 0, 160 o, oos O150 1! 1.2 3.5X10-'8.0X10-'3.0X10-' 0.015 0.100 0.025 0.25 HBS-2 Gelatin 1st O layer (yellow filter layer) Yellow colloidal silver X-5 B5- 1 Gelatin 11th layer (first blue-sensitive emulsion layer) Emulsion A Emulsion B Emulsion F Enhanced dye ■ X-9 X-8 1 (BS-1 Gelatin 12th layer (second blue-sensitive emulsion layer) Emulsion G Sensitizing dye ■ X-9 0,10 1,54 Silver 0.05 0.08 0.03 0.95 9 0.08 il 0.07 Silver 0.07 3.5X10-' 0.721 0.042 0.28 1 .10 Silver 0.45 2, lX10-' 0.154 X-10 B5-1 Gelatin 13th layer (third blue-sensitive emulsion layer) Emulsion H Sensitizing dye■ 1 protective layer) Emulsion I -4 -5 B5-1 Gelatin 15th layer (second protective layer) Polymethyl acrylate particles (diameter approximately 1.5 μm) -1 Gelatin 0.007 0.05 0.78 $1 0. 77 2.2 Curing agent H-1 and a surfactant were added.

X 1 X-2 H X-3 H X X-8 -2 -3 Sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ Shil -4 -5 B5-1 Tricresyl phosphate B5-2 Di-n-butyl phthalate sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ S-1 -1 CL=C)I SOX C)I! C0NHGH
zCHz=CHS(h CH2C0NHCH2 (Example-4a) Emulsion H of the 13th layer was mixed with emulsions (3-C) to (3-
G) was replaced with one chemically sensitized in the same manner as in Example-3,
Samples 401 to 405 were used. Example except that a blue filter was used for density measurement and the development time was changed as described above.
Sample 4o of the present invention, whose photographic performance was compared in the same manner as 3.
3 (emulsion 3E) and 405 (emulsion 3-G) are comparative samples 401 (emulsion 3-C), 402 (emulsion 3-D), and 4
Compared to Emulsion 04 (Emulsion 3-F), the results showed that the sensitivity was higher, the gradation was harder, and the change in photographic performance due to pressure was small.

(Example-4b) Emulsion E in the ninth layer was replaced with emulsions (3-C) to (3-G) with the same silver content.
) was replaced with samples 411 to 415. Emulsion (3-
C) to (3-G) are sensitizing dyes V, ■ prior to chemical sensitization.
, ■ were added and the amount of chemical sensitizer added was adjusted in the same manner as in Example 3. Samples 413 (emulsion 3-E) and 415 (emulsion 3-G) of the present invention were compared with the samples of comparative example in the same manner as in Example 3 except that the developing time was changed as described above. 411 (Emulsion 3-C).

Compared to 412 (Emulsion 3-D) and 414 (Emulsion 3-F), it showed higher sensitivity, harder gradation, and less change in photographic performance due to pressure.

(Example-4c) Emulsions (3-C) to (3-C) with the same silver content were used as emulsions in the fifth layer.
) was replaced with Samples 421 to 425. Emulsion (3
-C) to (3-G) are sensitizing dyes ■ prior to chemical sensitization;
The same procedure as in Example 3 was carried out except that (2) was added and the amount of chemical sensitizer added was adjusted. Sensitizing dye I was added immediately before coating. Sample 423 (emulsion 3-E) of the present invention was compared for photographic performance in the same manner as in Example 3, except that the development time was changed as described above and the density measurement was changed to a red filter.

425 (emulsion 3-G) is the comparative example sample 421 (emulsion 3-G).
C), 422 (emulsion 3-D), 424 (emulsion 3-F)
) showed higher sensitivity, harder gradation, and less change in photographic performance due to pressure.

[Brief explanation of drawings]

FIG. 1 shows the particle forming system, and FIG. 2 shows the mixer. 1: Reaction container 2: Protective colloid aqueous solution 3: Stirrer 4: Silver salt aqueous solution 5: Halogen salt aqueous solution 6: Protective colloid aqueous solution 7: Mixer 8: Transport system 9: Stirring blade IO: Reaction chamber 11: Rotating shaft No. 3 The figure is a photograph of a silver halide crystal with a fine ring-like striped pattern. 4 and 5(a) show examples of systems used in the present invention, and FIGS. 5(b), (c), and (d) show other examples of mixers. 24.257 Stirrer 26.30: Pumps 31 to 35: Flow rate needle 36.37: Mixing tank 38: Mixer 40: Reaction container 41: Protective colloid aqueous solution tank 42: Silver salt aqueous solution tank 43: Reserve tank 44 : Halogen salt aqueous solution tank 45 : Halogen salt aqueous solution tank 53 : Protective colloid aqueous solution tank 54 : Silver salt aqueous solution tanks 55 to 58 : Pumps 59 to 62 : Flow meter 63 : Mixer 64 : Reaction container 65.66 : Stirrer x 1: Tank for halogen aqueous solution that forms easily soluble silver halide x 2: Tank for halogen aqueous solution that forms poorly soluble silver halide

Claims (1)

[Claims] The light-sensitive silver halide grains contained in the silver halide photographic emulsion undergo a reaction by adding fine-sized silver halide grains into a reaction vessel in which nucleation and/or crystal growth of the grains occurs. These are photosensitive silver halide grains obtained by nucleation and/or crystal growth in a container, and the fine-sized silver halide grains are obtained by nucleation and/or crystal growth of the photosensitive silver halide grains. The photosensitive halogen is formed by mixing an aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide in a mixer installed outside a reaction vessel in which the photosensitive halogen The halide ions supplied to the nucleation and/or crystal growth of silver grain grains and contained in the water-soluble halide aqueous solution are composed of at least two of chloride ions, bromide ions and iodide ions. A method for producing a silver halide photographic emulsion, comprising the step of continuously changing the ratio of the amounts of the at least two halide ions added over time.